CN103566938A - Preparation method for preparing synthesis gas NiO@SiO2 core-shell type catalyst by employing low-concentration coalbed methane - Google Patents
Preparation method for preparing synthesis gas NiO@SiO2 core-shell type catalyst by employing low-concentration coalbed methane Download PDFInfo
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Abstract
The invention discloses a preparation method for preparing a synthesis gas NiO@SiO2 core-shell type catalyst by employing low-concentration coalbed methane, belongs to the technical fields of a natural gas chemical industry and a coal chemical industry, and mainly solves the problems of easy sintering and easy carbon deposit of an existing method for preparing a catalyst in the synthesis gas preparation process by employing the low-concentration coalbed methane. The method disclosed by the invention is characterized by comprising the following steps: firstly, preparing nanoscale NiO particles from a soluble nickel salt by adopting a thermal decomposition method; dispersing the nano particles into ethanol, and adding a soluble silicon source; decomposing and polymerizing the soluble silicon source, so as to form encapsulated microspheres containing NiO nano particles; and etching in an alkaline environment, and finally preparing a multi-channel core-shell type NiO@SiO2 catalyst. The core-shell type NiO@SiO2 catalyst prepared by the preparation method disclosed by the invention displays good sintering resistance and good coke formation resistance in a synthesis gas preparation reaction employing the low-concentration coalbed methane.
Description
Technical field
A kind of low concentration coal-bed gas preparing synthetic gas of the present invention NiOSiO
2the preparation method of hud typed catalyst, belongs to the field of gas chemical industry and coal chemical technology.
Background technology
Coal bed gas refers to be stored in is conigenous storage formula gas in coal seam certainly, and its active ingredient is methane.China is big coal country, and coal bed gas resource is very abundant, and reserves occupy third place in the world, but its utilization rate is very low.Coal bed gas can be divided into ground extraction and down-hole extraction coal bed gas, the coal bed gas CH of ground extraction according to extraction way
4content is in 85%(volume fraction, lower same) more than, be the main path that coal bed gas resourceization is utilized, but its scale is less.Down-hole extraction coal bed gas is the coal bed gas for mining safety extraction from mine, owing to infiltrating large quantity of air in pump drainage process, causes CH
4concentration reduces.Generally by CH
4the extraction coal bed gas of concentration < 35% is called low concentration coal-bed gas, and the processing method of current most mines is directly discharge, has not only wasted resource, and has aggravated greenhouse effects.
Due to the difference of colliery mining conditions and ature of coal, the low concentration coal-bed gas of down-hole extraction composition and content are slightly different.Common CH
4content is between 5 ~ 35%, and all the other are mixing air (N
2and O
2) and a small amount of H
2o, H
2s, CO
2deng gas.In coal bed gas, sour gas is (as H
2s and CO
2deng) and water more easily remove, O
2take second place, the gas of difficult separation is N
2.Because N
2physical property and CH
4very approaching, adopt the physical method for separation efficiency such as freezing separation, membrane technology and pressure-variable adsorption very low, and energy consumption is very large.All not yet obtain at present industrial applications.
For CH
4the low concentration coal-bed gas of content 25 ~ 35%, because of its CH
4/ O
2proportioning approach 2:1, can be by CH
4by partial oxidation, make synthesis gas.In view of CH
4partial oxidation be gentle exothermic reaction, be not prone to " temperature runaway " phenomenon, and N
2as carrier gas, can reduce the bed hot(test)-spot temperature of reactor, so N
2existence favourable for this reaction.The mix products obtaining after low concentration coal-bed gas catalytic reaction is synthesis gas and N
2mist, can be used for that dimethyl ether is synthetic, low pressure F-T liquid hydrocarbon synthetic and supercritical phase methyl alcohol synthetic etc.; Also can be according to the difference of physical property in system, by stage variable pressure absorption method etc., relatively easily by component H wherein
2, CO and N
2progressively separated; Also can further obtain hydrogen through water vapour conversion, then separated etc. again.
Partial oxidation reaction of methane catalyst used is mainly divided into two classes at present: a class is loaded noble metal catalyst, better catalytic activity, but because cost is high, be unfavorable for industrial application; Another kind of is that support type Ni, Co are catalyst based, and because its activity is higher, cheap, and productive rate is high under high-speed operating condition, has tempting industrial applications prospect, receives researcher's very big concern.At present, most study be that support type Ni is catalyst based, although reaction can under high temperature, high-speed, obtain high conversion ratio, there is the universal phenomenon of catalyst activity component easy-sintering and carbon deposit, affected the service life of catalyst, thereby limited it, applied.Chinese patent CN101693203 discloses a kind of hydro-thermal legal system of using for ZrO
2, and be used as the catalyst based carrier of Ni through high-temperature process, it is said that this catalyst has good stability and anti-Coking Behavior.Chinese patent CN101890352 discloses the catalyst based preparation method of Co, and this catalyst is usingd Co as active component, and general formula is Co-Me-Al
2o
3, in formula, Me represents alkaline-earth metal, with the form of oxide, exists, and it is said active component high degree of dispersion, not easy-sintering and loss.Although can improve catalytic activity to a certain extent by introducing other metal promoters, carbon distribution and the Sintering Problem of catalyst are not solved at all.
Chinese patent CN101623634 has proposed a kind of preparation method of core-shell nano catalyst of coating noble metal nano particle, and first the method makes noble metal nano particles, by microwave method, makes noble metal-iron oxide hetero-junctions, and this nano particle is carried out to SiO
2layer, SnO
2layer and C layer are coated, by sacrificing iron oxide, obtain nucleocapsid structure.The method operating process is complicated, and core core is divided into noble metal, because acid solution is inoperative to noble metal to erode iron oxide only, so to the control of noble metal nano particles particle diameter difficulty comparatively.
Summary of the invention
A kind of low concentration coal-bed gas preparing synthetic gas of the present invention NiOSiO
2the preparation method of hud typed catalyst, object is to disclose a kind of hud typed clad structure and can suppresses core core active component and at high temperature move and reunite, fundamentally solve the Sintering Problem existing in above-mentioned prior art, shell duct is regulated and controled simultaneously, regulate active component surface reaction speed, play a kind of method of utilizing thermal decomposition to prepare common metal nano particle nucleocapsid structure that suppresses carbon deposit effect, operating process is simpler, and can accurately control particle diameter, to improve anti-sintering and the anti-carbon deposit of active component, thereby improve the method for preparing catalyst of catalytic activity and the low concentration coal-bed gas preparing synthetic gas in life-span, also provide a kind of coal bed gas to be converted into the method for synthesis gas simultaneously.
A kind of low concentration coal-bed gas preparing synthetic gas of the present invention NiOSiO
2the preparation method of hud typed catalyst, it is characterized in that a kind of hud typed clad structure can suppress core core active component and at high temperature moves and reunite, fundamentally solve Sintering Problem, shell duct regulated and controled, regulated active component surface reaction speed, play and suppress carbon deposit effect and utilize thermal decomposition to prepare the low concentration coal-bed gas preparing synthetic gas NiOSiO of common metal nano particle nucleocapsid structure simultaneously
2the method of hud typed catalyst, its manufacturing process is as follows:
1) take 1 ~ 10g soluble metal nickel salt, 10 ~ 20g polyvinylpyrrolidone, is dissolved in 100ml pentanediol solution;
2) at N
2under protection, above-mentioned solution is heated to 100 ~ 200 ℃, under constant temperature, stirs 3 ~ 4h, then solution is continued to be heated to 200 ~ 300 ℃, constant temperature stirs 1 ~ 2h, then naturally cools to room temperature;
3) add 100 ~ 200ml acetone soln, be precipitated, centrifugation gained precipitation, and clean gains with ethanol, then by gained nanoparticulate dispersed in 100ml ethanolic solution;
4) SiO of NiO nano particle outer cladding multi-pore channel
2the preparation method of shell comprises the steps:
First, measure the ethanolic solution 5 ~ 10ml of the dispersing nanoparticles described in step 3), in this solution, add 1 ~ 2g polyvinylpyrrolidone, under room temperature, stir 12 ~ 24h; Then, add 10 ~ 20ml ammonia spirit, be placed in the ultrasonic concussion 30 ~ 60min of ultrasonator; Finally, then add 0.1 ~ 1ml soluble silicon source and 5 ~ 10ml ethanolic solution, continue sonic oscillation 1 ~ 2h; Centrifugal collection product, washes it respectively and ethanol cleans; Product being placed in to pH is etching 12 ~ 24h under 7 ~ 14 alkaline environments again, by gains dry 2 ~ 6h in vacuum drying chamber, makes the NiOSiO of multi-pore channel
2hud typed catalyst.
Above-mentioned a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO
2the preparation method of hud typed catalyst, is characterized in that described soluble silicon source is methyl silicate or ethyl orthosilicate.
Above-mentioned a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO
2the preparation method of hud typed catalyst, is characterized in that, described alkaline environment is KOH, NaOH, NaCO
3and NH
3h
2a kind of solution in O or multiple solution mix.
Use above-mentioned a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO
2the prepared NiOSiO of preparation method of hud typed catalyst
2catalyst, under constant-pressure and high-temperature, can be in synthesis gas or the reaction that is applied in other methane portion oxidation synthesis gas, to have the performance of anti-carbon deposit and anti-sintering by low concentration coal-bed gas Efficient Conversion.
A kind of low concentration coal-bed gas preparing synthetic gas of the present invention NiOSiO
2the preparation method of hud typed catalyst has following outstanding feature:
(1) catalytic reaction occurs being positioned on the nanoparticle core at center, and the size of nanoparticle core, form and surface texture can be at SiO
2precisely controlled before parcel;
(2) reactant, product passes through SiO
2the duct diffusion of shell is carried out, and its diffusion rate can regulate by adjusting hole density and average pore size;
(3) environment of active particle is single, and NiO kernel is through H
2reduction, produces space with shell, can be reaction enough space and catalytic surfaces are provided.
Accompanying drawing explanation
Fig. 1 is to be the electromicroscopic photograph through the made NiO nano particle of thermolysis process;
Fig. 2 is the hud typed NiOSiO through coated
2the electromicroscopic photograph of catalyst;
The NiOSiO that Fig. 3 is
2hud typed catalyst and traditional infusion process NiO/SiO
2the methane conversion comparison diagram of catalyst under same reaction condition.
The NiOSiO that Fig. 4 is
2hud typed catalyst and traditional infusion process NiO/SiO
2the carbon monoxide selective comparison diagram of catalyst under same reaction condition.
The NiOSiO that Fig. 5 is
2hud typed catalyst and traditional infusion process NiO/SiO
2the hydrogen selective comparison diagram of catalyst under same reaction condition.
The NiOSiO that Fig. 6 is
2hud typed catalyst and traditional infusion process NiO/SiO
2the H of catalyst under same reaction condition
2/ CO ratio comparison diagram.
the specific embodiment
embodiment 1
catalyst preparation:take 2.1g soluble metal nickel salt, 10.7g polyvinylpyrrolidone, is dissolved in 100ml pentanediol solution.At N
2under protection, above-mentioned solution is heated to 200 ℃, and stirs 4h at this temperature, then solution is continued to be heated to 270 ℃, stir 1h, be cooled to room temperature.Add 100ml acetone soln, be precipitated, centrifugation gained precipitation, and clean gains with ethanol, by gained nanoparticulate dispersed in 100ml ethanol.The ethanolic solution of getting nanoparticulate dispersed in the upper step of 100ml adds 1g polyvinylpyrrolidone in solution, under room temperature, stirs 12h.In above-mentioned solution, add 10ml ammonia spirit, be placed in sonic oscillation instrument 30min.In above-mentioned solution, add 0.1ml ethyl orthosilicate, 5ml ethanolic solution, continue sonic oscillation 1h.Centrifugal collection product, and to its washing, alcohol wash, by product under alkaline environment (PH=11) etching 24h, gains are placed in after the dry 5h of vacuum drying chamber, make multi-pore channel NiOSiO
2catalyst.
catalytic performance test:catalytic reaction is reacted in fixed bed reactors.Before reaction, catalyst first at 750 ℃ with H
2reductase 12 h; Then pass into unstripped gas, it forms CH
4/ O
2/ N
2be 2/1/2 (mol ratio), normal pressure, 750 ℃ of reaction temperatures, air speed is constant is 5 * 10
4mlh
-1g
-1, product is used gas chromatographic analysis after condensation dewaters.The experimental result of embodiment 1 is as shown in table 1.
Table 1 NiOSiO
2on catalyst (750 ℃ of reduction are processed), carry out the experimental result of coal bed gas transformation of synthetic gas
embodiment 2
catalyst preparation:
Take 4.3g soluble metal nickel salt, 16g polyvinylpyrrolidone, is dissolved in 100ml pentanediol solution.At N
2under protection, above-mentioned solution is heated to 170 ℃, and stirs 2.5h at this temperature, then solution is continued to be heated to 200 ℃, stir 1.5h, be cooled to room temperature.Add 150ml acetone soln, be precipitated, centrifugation gained precipitation, and clean gains with ethanol, by gained nanoparticulate dispersed in 200ml ethanol.The ethanolic solution of getting nanoparticulate dispersed in the upper step of 100ml adds 1.6g polyvinylpyrrolidone in solution, under room temperature, stirs 12h.In above-mentioned solution, add 17ml ammonia spirit, be placed in sonic oscillation instrument 30min.In above-mentioned solution, add 0.5ml ethyl orthosilicate, 10ml ethanolic solution, continue sonic oscillation 1h.Centrifugal collection product, and to its washing, alcohol wash, gains are placed in after the dry 4h of vacuum drying chamber, make micropore NiOSiO
2catalyst.
catalytic performance test condition:with reference to embodiment 1, evaluation result is in Table 2.
Table 2 micropore NiOSiO
2catalyst catalytic performance
embodiment 3
catalyst preparation: reference example 1;
catalytic performance test:catalytic reaction is reacted in fixed bed reactors.Before reaction, catalyst first at 750 ℃ with H
2reductase 12 h; Then pass into unstripped gas, it forms CH
4/ O
2/ N
2be 2/1/2 (mol ratio), normal pressure, 750 ℃ of reaction temperatures, air speed is constant is 1 * 10
5mlh
-1g
-1, product is used gas chromatographic analysis after condensation dewaters.The experimental result of embodiment 3 is as shown in table 3.
Table 3 NiOSiO
2the catalytic performance of catalyst under different air speed conditions
Claims (4)
1. a low concentration coal-bed gas preparing synthetic gas NiOSiO
2the preparation method of hud typed catalyst, it is characterized in that a kind of hud typed clad structure can suppress core core active component and at high temperature moves and reunite, fundamentally solve Sintering Problem, shell duct regulated and controled, regulated active component surface reaction speed, play and suppress carbon deposit effect and utilize thermal decomposition to prepare the low concentration coal-bed gas preparing synthetic gas NiOSiO of common metal nano particle nucleocapsid structure simultaneously
2the method of hud typed catalyst, its manufacturing process is as follows:
1) take 1 ~ 10g soluble metal nickel salt, 10 ~ 20g polyvinylpyrrolidone, is dissolved in 100ml pentanediol solution;
2) at N
2under protection, above-mentioned solution is heated to 100 ~ 200 ℃, under constant temperature, stirs 3 ~ 4h, then solution is continued to be heated to 200 ~ 300 ℃, constant temperature stirs 1 ~ 2h, then naturally cools to room temperature;
3) add 100 ~ 200ml acetone soln, be precipitated, centrifugation gained precipitation, and clean gains with ethanol, then by gained nanoparticulate dispersed in 100ml ethanolic solution;
4) SiO of NiO nano particle outer cladding multi-pore channel
2the preparation method of shell comprises the steps:
First, measure the ethanolic solution 5 ~ 10ml of the dispersing nanoparticles described in step 3), in this solution, add 1 ~ 2g polyvinylpyrrolidone, under room temperature, stir 12 ~ 24h; Then, add 10 ~ 20ml ammonia spirit, be placed in the ultrasonic concussion 30 ~ 60min of ultrasonator; Finally, then add 0.1 ~ 1ml soluble silicon source and 5 ~ 10ml ethanolic solution, continue sonic oscillation 1 ~ 2h; Centrifugal collection product, washes it respectively and ethanol cleans; Product being placed in to pH is etching 12 ~ 24h under 7 ~ 14 alkaline environments again, by gains dry 2 ~ 6h in vacuum drying chamber, makes the NiOSiO of multi-pore channel
2hud typed catalyst.
2. according to a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO described in claim 1
2the preparation method of hud typed catalyst, is characterized in that described soluble silicon source is methyl silicate or ethyl orthosilicate.
3. according to a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO described in claim 1
2the preparation method of hud typed catalyst, is characterized in that, described alkaline environment is KOH, NaOH, NaCO
3and NH
3h
2a kind of solution in O or multiple solution mix.
Right to use require 1 described in a kind of low concentration coal-bed gas preparing synthetic gas NiOSiO
2the prepared NiOSiO of preparation method of hud typed catalyst
2catalyst, is characterized in that prepared NiOSiO
2catalyst, under constant-pressure and high-temperature, can be in synthesis gas or the reaction that is applied in other methane portion oxidation synthesis gas, to have the performance of anti-carbon deposit and anti-sintering by low concentration coal-bed gas Efficient Conversion.
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| CN104056635A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method for catalyst for preparing synthetic gas by virtue of low-temperature partial oxidation of methane |
| CN109317149A (en) * | 2018-10-11 | 2019-02-12 | 郑州大学 | A kind of SiO of nickel-loaded2The preparation method and application of@C core-shell material |
| CN109331813A (en) * | 2018-11-02 | 2019-02-15 | 中国科学院重庆绿色智能技术研究院 | Catalyst, preparation method, catalysis Enhancement Method, purification device |
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| CN112275278A (en) * | 2020-04-07 | 2021-01-29 | 杭州电子科技大学 | Shell-core type composite nano material with hollow silicon sphere layer as shell and nano metal oxide as core, and preparation method and application thereof |
| CN112452328A (en) * | 2020-11-06 | 2021-03-09 | 上海簇睿低碳能源技术有限公司 | NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst |
| CN113842940A (en) * | 2021-09-27 | 2021-12-28 | 太原理工大学 | Catalyst for preparing methanol by low-temperature conversion of low-concentration coal bed gas and method for preparing methanol |
| CN115259085A (en) * | 2022-07-04 | 2022-11-01 | 广东能源集团科学技术研究院有限公司 | Preparation method of high-purity hydrogen |
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| CN104056633A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method of SiO2-coated core-shell structure catalyst |
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| CN109482176A (en) * | 2018-11-02 | 2019-03-19 | 中国科学院重庆绿色智能技术研究院 | Catalyst and preparation method thereof |
| CN112275278A (en) * | 2020-04-07 | 2021-01-29 | 杭州电子科技大学 | Shell-core type composite nano material with hollow silicon sphere layer as shell and nano metal oxide as core, and preparation method and application thereof |
| CN112275278B (en) * | 2020-04-07 | 2022-05-17 | 杭州电子科技大学 | Shell-core type composite nano material with hollow silicon sphere layer as shell and nano metal oxide as core, and preparation method and application thereof |
| CN112452328A (en) * | 2020-11-06 | 2021-03-09 | 上海簇睿低碳能源技术有限公司 | NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst |
| CN113842940A (en) * | 2021-09-27 | 2021-12-28 | 太原理工大学 | Catalyst for preparing methanol by low-temperature conversion of low-concentration coal bed gas and method for preparing methanol |
| CN115259085A (en) * | 2022-07-04 | 2022-11-01 | 广东能源集团科学技术研究院有限公司 | Preparation method of high-purity hydrogen |
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